WO2012176471A1 - Poudre d'oxyde complexe contenant du lithium et son procédé de production - Google Patents

Poudre d'oxyde complexe contenant du lithium et son procédé de production Download PDF

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WO2012176471A1
WO2012176471A1 PCT/JP2012/004070 JP2012004070W WO2012176471A1 WO 2012176471 A1 WO2012176471 A1 WO 2012176471A1 JP 2012004070 W JP2012004070 W JP 2012004070W WO 2012176471 A1 WO2012176471 A1 WO 2012176471A1
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lithium
composite oxide
containing composite
oxide powder
molten salt
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English (en)
Japanese (ja)
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祐樹 杉本
直人 安田
史弥 金武
英明 篠田
三好　学
木下　恭一
阿部　徹
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株式会社豊田自動織機
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Priority to US14/128,744 priority Critical patent/US20140134491A1/en
Publication of WO2012176471A1 publication Critical patent/WO2012176471A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/06—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using as solvent a component of the crystal composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium-containing composite oxide powder mainly used as a positive electrode material of a lithium ion secondary battery and a non-aqueous electrolyte secondary battery using the lithium-containing composite oxide powder.
  • a lithium ion secondary battery has an active material capable of inserting and removing lithium (Li) in each of a positive electrode and a negative electrode. Then, it operates by moving Li ions in the electrolyte provided between both electrodes.
  • the performance of the lithium ion secondary battery depends on the materials of the positive electrode, the negative electrode and the electrolyte that constitute the lithium ion secondary battery. Among them, research and development of active material materials forming active materials are being actively conducted. For example, lithium-containing containing a positive electrode active as the material, Li 2 MnO 3, LiCoO 2 , LiNiO 2, lithium and another metal element having a layered rock salt structure of alpha-NaFeO 2 type, such as LiFeO 2 of the lithium ion secondary battery Complex oxides are known.
  • a solid phase method as a method of producing the lithium-containing composite oxide.
  • a Ni—Mn—Co complex oxide powder (the molar ratio of Ni / Mn / Co is 1/1/1) and a lithium hydroxide monohydrate powder are obtained by LiCo 1/3 Ni 1/3 Mn 1/3 O 2 is synthesized by mixing Ni + Mn + Co) at a molar ratio of 1.02 and holding the mixture at 1000 ° C. for 15 hours.
  • the obtained lithium-containing composite oxide is a secondary particle in which a plurality of primary particles having an average particle diameter of 1.1 ⁇ m are aggregated.
  • the lithium-containing composite oxide synthesized by the solid phase method is composed of secondary particles in which a plurality of fine particles are aggregated, in other words, polycrystalline particles composed of a plurality of crystal grains.
  • the single crystal is obtained by the solid phase method similar to the above.
  • LiNiO 2 powder is synthesized.
  • the lithium-containing composite oxide synthesized by the solid phase method is a polycrystal composed of a plurality of crystal grains.
  • the obtained fired product includes secondary particles in which crystal grains of a large size are aggregated. It is guessed.
  • the fired product is pulverized and classified to obtain a LiNiO 2 powder composed of single crystals having an average particle diameter of 10 ⁇ m or less.
  • the Li 2 MnO 3 thus obtained is described to be a plate-like single crystal of about 0.3 mm.
  • the synthesis method described in Patent Document 3 is a so-called molten salt method, and is a method generally used to synthesize a fine lithium-containing composite oxide.
  • the lithium-containing composite oxide synthesized by the solid phase method is, as described above, a powder composed of polycrystalline particles. There are many grain boundaries in polycrystalline grains. In general, grain boundaries are a kind of defects and thus cause the collapse of particles. Further, in the crystal grain boundaries, an impurity having a composition different from that of the target lithium-containing composite oxide is present.
  • a lithium ion secondary battery using, as a positive electrode active material a powder of a lithium-containing composite oxide synthesized by such a solid phase method
  • particles of the lithium-containing composite oxide form crystal grain boundaries with repeated charging and discharging. It is easily disintegrated, and when the lithium ion secondary battery is operated at a high voltage, impurities present in grain boundaries become active points of electrolyte decomposition. Such a phenomenon leads particularly to deterioration of cycle characteristics among the characteristics of the secondary battery.
  • Patent Document 2 polycrystalline particles of LiNiO 2 synthesized by the solid phase method are pulverized to obtain LiNiO 2 powder. That is, it can be said that the collapse of particles accompanying charge and discharge is suppressed by using a powder that has been disintegrated in advance.
  • the pulverized LiNiO 2 powder may contain single crystals of single crystals formed by being crushed at grain boundaries.
  • the pulverized LiNiO 2 powder has problems such as contamination of impurities present in polycrystalline particles and inclusion of polycrystalline single particles depending on the degree of pulverization.
  • Li 2 MnO 3 disclosed in Patent Document 3 is a single crystal grown by a molten salt method.
  • Patent Document 3 aims to grow a large single crystal of, for example, about 0.3 mm which can be used for a micro battery or a micro electrode. That is, the size of the single crystal grown in Patent Document 3 is so large that it is different from the particle size desired for a positive electrode active material such as a lithium ion secondary battery.
  • the present inventors have synthesized fine-grained Li 2 MnO 3 powder by the molten salt method for the purpose of using not only the surface but also the whole particle as an active material for lithium manganese-based oxides.
  • the particle diameter of the Li 2 MnO 3 powder is too small, the Li 2 MnO 3 powder is difficult to be aggregated and uniformly dispersed in the active material layer at the time of preparation of the electrode, and the fine particles are densely filled in the active material layer. It is difficult to Furthermore, very small particles, even single crystals, can not be said to have good crystallinity.
  • An object of the present invention is to provide a lithium-containing composite oxide powder suitable as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, and a method for producing the same.
  • the lithium-containing composite oxide powder of the present invention is produced by a molten salt method, and includes single crystal particles comprising a lithium-containing composite oxide containing at least lithium and one or more other metal elements and having a crystal structure belonging to a layered rock salt structure. And an average primary particle size of 200 nm or more and 30 ⁇ m or less.
  • the molten salt method is, in a broad sense, a method of growing crystals using a high temperature solution containing a molten salt of an inorganic salt as a solvent.
  • the molten salt method in the present invention is a method of synthesizing a target compound in a high temperature solution containing at least lithium and another metal element.
  • the single crystal particles are preferably particles consisting of a single crystal synthesized in a molten salt of lithium hydroxide.
  • the lithium-containing composite oxide powder according to the present invention is composed of single crystal particles and has no crystal grain boundary, and when used as a positive electrode active material of a non-aqueous electrolyte secondary battery, collapse of active material particles due to charge and discharge The decomposition of the electrolyte is suppressed.
  • the lithium-containing composite oxide powder of the present invention is composed of particles of relatively large size, it can be uniformly and densely packed in the active material layer. As a result, a non-aqueous electrolyte secondary battery exhibiting excellent cycle characteristics and high capacity can be obtained.
  • the present invention is also a method for producing a lithium-containing composite oxide powder according to the present invention, wherein the metal-containing raw material containing a metal element is lithium having a molar ratio exceeding the theoretical composition of lithium contained in the lithium-containing composite oxide. And a cooling step for cooling the molten salt after the single crystal growth step, and the lithium-containing complex oxidation produced. And a recovery step of recovering the material from the solid after cooling.
  • the powder which consists of lithium containing complex oxide which has 2 or more types of metallic elements which make Li essential and whose crystal structure belongs to a layered rock salt structure is obtained.
  • a lithium manganese-based oxide essentially containing lithium and manganese as the lithium-containing composite oxide can be mentioned. If the lithium manganese-based oxide has a layered rock salt structure, the average oxidation number of Mn is basically tetravalent, but the composition of the lithium-containing composite oxide in the present invention may slightly deviate from the basic composition. The average oxidation number of Mn of the manganese-based oxide is allowed to be 3.8 to 4.
  • the lithium-containing composite oxide may be a lithium nickel oxide having a crystal structure belonging to a layered rock salt structure, and if the lithium nickel oxide is a layered rock salt structure, basically the average oxidation number of Ni is trivalent However, the average oxidation number of lithium nickel-based oxide Ni can be 2.8 to 3.
  • the lithium-containing composite oxide may be a lithium cobalt-based oxide whose crystal structure belongs to a layered rock salt structure, or may be a lithium iron-based oxide whose crystal structure belongs to a layered rock salt structure.
  • lithium cobalt-based oxides and lithium iron-based oxides have a layered rock salt structure, basically the average oxidation number of Co and Fe is trivalent, but Co of lithium cobalt-based oxides and Fe of lithium iron-based oxides
  • the average oxidation number of is allowed to be 2.8 to 3.
  • lithium-containing composite oxides Li 2 MnO 3 , LiCoO 2 , LiNiO 2 , LiFeO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.5 O 2 , Etc.
  • the composition formula of these lithium-containing composite oxides is xLi 2 M 1 O 3.
  • M 1 is a kind having a tetravalent Mn as an essential element.
  • the above metal element, M 2 is one or more metal elements essentially containing at least one of trivalent Co, trivalent Ni and trivalent Fe or two or more kinds metal elements essentially comprising tetravalent Mn) Is represented by
  • the lithium-containing composite oxide powder obtained by the production method of the present invention can be used as a positive electrode active material of a secondary battery such as a lithium ion secondary battery. That is, the present invention can also be grasped as a positive electrode active material for a non-aqueous electrolyte secondary battery comprising the lithium-containing composite oxide powder of the present invention.
  • the lithium-containing composite oxide powder of the present invention is used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, battery characteristics such as cycle characteristics of the non-aqueous electrolyte secondary battery are improves.
  • the Li 2 MnO 3 powder is a lithium-containing composite oxide powder of the present invention is a drawing-substitute photograph showing a result of observation by a scanning electron microscope (SEM).
  • the Li 2 MnO 3 powder is a lithium-containing composite oxide powder of the present invention is a drawing-substitute photograph showing a result of observation by SEM. It is a drawing substitute photograph which shows the result of having observed the LiCoO 2 powder which is lithium containing complex oxide powder of this invention by SEM. It is a drawing substitute photograph which shows the result of having observed LiNiO 2 powder which is lithium content complex oxide powder of the present invention by SEM.
  • the LiCoO 2 powder is a lithium-containing composite oxide powder of the present invention is a graph showing the charge-discharge characteristics of the secondary battery using as the positive electrode active material. It is a graph which shows the charge / discharge characteristic of the secondary battery which used LiCo 1/3 Ni 1/3 Mn 1/3 O 2 powder which is lithium containing complex oxide powder of this invention as a positive electrode active material. It is a differential scanning calorimetry curve of the lithium containing complex oxide powder of this invention in charge condition, and the conventional lithium containing complex oxide powder in charge condition.
  • the numerical range “a to b” described in the present specification includes the lower limit a and the upper limit b in that range. Then, the upper limit value and the lower limit value, and the numerical values listed in the examples can be combined arbitrarily to constitute a numerical range.
  • the lithium-containing composite oxide powder of the present invention contains single crystal particles composed of a lithium-containing composite oxide containing at least Li and one or more other metal elements and having a crystal structure belonging to a layered rock salt structure.
  • the composition formula of the lithium-containing composite oxide having a crystal structure belonging to the layered rock salt structure is xLi 2 M 1 O 3.
  • LiM 2 O 2 (0 ⁇ x ⁇ 1, where M 1 is one or more metal elements essentially including tetravalent Mn, M 2 is trivalent Co, trivalent Ni and trivalent Of at least one kind of Fe of the above, or two or more kinds of metal elements of the essential elements of tetravalent Mn).
  • part of Li may be substituted with H, and Li in an atomic ratio of 60% or less, and further 45% or less may be substituted with H.
  • M 1 be almost tetravalent Mn
  • M 1 may be substituted by less than 50% or less than 80% by another metal element.
  • M 2 is preferably mostly trivalent Co, trivalent Ni or trivalent Fe, but M 2 may be substituted by less than 50% or even less than 80% by another metal element.
  • the substituting element at least one metal element selected from Ni, Al, Co, Fe, Mg, and Ti is preferable from the viewpoint of the chargeable / dischargeable capacity in the case of using the electrode material.
  • the lithium-containing composite oxide is based on the above compositional formula, and needless to say, lithium which is slightly deviated from the above compositional formula due to unavoidable defects of Li, M 1 , M 2 or O. Also includes contained complex oxides.
  • the lithium-containing composite oxide has a composition formula: Li 1.33 -y M 1 0.67 -z M 2 y + z O 2 (wherein M 1 is one or more metal elements that essentially have tetravalent Mn, M 2 Is one or more metallic elements essentially containing at least one of trivalent Co, trivalent Ni and trivalent Fe, or two or more kinds of metallic elements essentially comprising tetravalent Mn, 0 ⁇ y ⁇ 0.33 , 0 ⁇ z ⁇ 0.67).
  • M 1 is one or more metal elements that essentially have tetravalent Mn
  • M 2 Is one or more metallic elements essentially containing at least one of trivalent Co, trivalent Ni and trivalent Fe, or two or more kinds of metallic elements essentially comprising tetravalent Mn, 0 ⁇ y ⁇ 0.33 , 0 ⁇ z ⁇ 0.67).
  • M 1 is one or more metal elements that essentially have tetravalent Mn
  • M 2 Is one or more
  • lithium-containing composite oxides LiCoO 2 , LiNiO 2 , LiFeO 2 , Li 2 MnO 3 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.5 Examples thereof include O 2 and solid solutions containing two or more of them.
  • the composition formula of the lithium-containing composite oxide may be any of those exemplified composition formulas as a basic composition, and a part of Mn, Fe, Co and Ni is substituted with another metal element. It is also good. A part of Li may be replaced by H.
  • the composition formula of the lithium-containing composite oxide may be slightly deviated from the above composition formula due to the deficiency of the metal element or oxygen which inevitably occurs.
  • a lithium-containing composite oxide having a basic composition of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , Li 2 MnO 3 , LiNiO 2 or the like as a positive electrode active material of a non-aqueous electrolyte secondary battery When used, it may be used with high cutoff voltage (for example, 4.4 V or more in Li standard). Degradation of the electrolyte is likely to occur at high voltages. Therefore, in the non-aqueous electrolyte secondary battery using the lithium-containing composite oxide powder of the present invention having these compositions, the effect of suppressing the decomposition of the electrolyte becomes even more remarkable.
  • Identification of the structure and composition of the above lithium-containing composite oxide can be made by X-ray diffraction (XRD), electron diffraction, emission spectroscopy (ICP) and the like. Further, in a high resolution image using a high resolution transmission electron microscope (TEM), even if the sample is a relatively large particle, the layer structure can be observed by micro-processing the sample.
  • XRD X-ray diffraction
  • ICP emission spectroscopy
  • TEM transmission electron microscope
  • the lithium-containing composite oxide powder of the present invention has an average primary particle size of 200 nm or more and 30 ⁇ m or less.
  • the average primary particle size is determined by measuring the maximum diameter of a plurality of particles (the maximum value of the distance between parallel lines when the particles are sandwiched between two parallel lines) from a micrograph such as SEM. Average value.
  • Powders having an average primary particle size of 200 nm or more are easy to handle industrially. Specifically, in the powder having an average primary particle diameter of 200 nm or more, aggregation of particles is suppressed at the time of preparation of the electrode, and it is easy to be uniformly dispersed in the active material layer.
  • the powder having an average primary particle size of 200 nm or more has high crystallinity, it is excellent in characteristics such as the filling property and the thermal stability in the active material layer.
  • the average primary particle size is 300 nm or more and 500 nm or more, and more preferably 1 ⁇ m or more.
  • the average primary particle size is too large, the surface contributing to the battery reaction in contact with the electrolytic solution decreases, but by setting the average primary particle size to 30 ⁇ m or less, sufficient in terms of capacity, rate characteristics, etc. Battery characteristics are obtained.
  • the average primary particle size is 25 ⁇ m or less, preferably 20 ⁇ m or less, and more preferably 13 ⁇ m or less.
  • single crystal particles preferably consist of single particles.
  • the lithium-containing composite oxide powder of the present invention preferably contains single crystal single particles produced by the molten salt method.
  • single particle refers to a particle composed of a single particle not including a grain boundary, unlike a secondary particle formed by aggregation of a plurality of polycrystalline particles or fine particles composed of a plurality of crystal grains.
  • the fact that a single particle is a single crystal can be known, for example, by analysis of an electron beam diffraction image by a transmission electron microscope.
  • the specific surface area is preferably 0.5 m 2 / g or more and 20 m 2 / g or less.
  • the lithium-containing composite oxide powder of the present invention is a powder containing polycrystals (secondary particles) consisting of a plurality of fine crystal grains and single particles close to a single crystal obtained by pulverizing polycrystals (for example, In contrast to the above description, it consists of single crystal particles, preferably single crystals of single crystals, grown in a molten salt by the molten salt method. Therefore, the specific surface area of the lithium-containing composite oxide powder of the present invention is relatively small.
  • a further preferable specific surface area is 0.5 m 2 / g to 15 m 2 / g, 1 m 2 / g to 10 m 2 / g, and further 1.5 m 2 / g to 7 m 2 / g.
  • the above-mentioned specific surface area a value obtained by measuring a lithium-containing composite oxide powder by a BET method is adopted.
  • the method for producing a lithium-containing oxide powder mainly includes a single crystal growth step, a cooling step and a recovery step, and optionally includes a raw material preparation step, a precursor synthesis step and / or a firing step.
  • the metal-containing raw material and the molten salt raw material may be mixed.
  • the metal-containing raw material is a raw material for supplying one or more metal elements other than Li.
  • the valence of the metallic element contained in a metal containing raw material is preferably equal to or less than the valence of the metal element contained in the target lithium-containing composite oxide. This is because, in the method for producing a lithium-containing composite oxide powder according to the present invention, a single crystal is grown in a molten salt of lithium hydroxide in a high oxidation state, so, for example, divalent or trivalent Mn in the state of a raw material Even in the case of tetravalent Mn during the reaction.
  • the metal-containing raw material is a common single metal, metal compound or the like used in the molten salt method, it can be used. Specifically, if it is a Mn source, manganese dioxide (MnO 2 ), dimanganese trioxide (Mn 2 O 3 ), manganese monoxide (MnO), tetramanganese tetraoxide (Mn 3 O 4 ), hydroxylation Manganese (Mn (OH) 2 ), manganese oxyhydroxide (MnOOH), etc. may be mentioned.
  • Mn source manganese dioxide (MnO 2 ), dimanganese trioxide (Mn 2 O 3 ), manganese monoxide (MnO), tetramanganese tetraoxide (Mn 3 O 4 ), hydroxylation Manganese (Mn (OH) 2 ), manganese oxyhydroxide (MnOOH), etc.
  • Co source cobalt oxide (CoO, Co 3 O 4) , cobalt nitrate (Co (NO 3) 2 ⁇ 6H 2 O), cobalt hydroxide (Co (OH) 2), cobalt chloride (CoCl 2 ⁇ 6H 2 O), cobalt sulfate (Co (SO 4 ) ⁇ 7H 2 O), and the like.
  • Ni source nickel oxide (NiO), nickel nitrate (Ni (NO 3 ) 2 ⁇ 6H 2 O), nickel sulfate (NiSO 4 ⁇ 6H 2 O), nickel chloride (NiCl 2 ⁇ 6H 2 O), Etc.
  • a metal compound in which a part of the metal element contained in these oxides, hydroxides or metal salts is substituted with another metal element (eg, Cr, Mn, Fe, Co, Ni, Al, Mg, etc.) May be
  • Ni (OH) 2 Fe source if Co (OH) 2, Ni source if MnO 2, Co source if Mn source Fe (OH) 3 is preferable, and they are easy to obtain and relatively easy to obtain.
  • lithium-containing composite oxide powder containing two or more metal elements, and a metal element other than Li is substituted by another metal element
  • a lithium-containing composite oxide powder can be produced.
  • the metal-containing raw material contains two or more metal elements
  • a water-soluble inorganic salt specifically, nitrates, sulfates, chlorides and the like of metal elements are dissolved in water, and alkali metal hydroxide, ammonia water, etc. make the aqueous solution alkaline. Is produced as a precipitate.
  • the lithium-containing composite oxide to be synthesized is a lithium-nickel-based composite oxide containing Ni
  • formation of a by-product (NiO) which is difficult to remove by adopting a production method using a precursor It is preferable to adopt a manufacturing method using a precursor because
  • the molten salt raw material mainly contains lithium hydroxide.
  • State lithium hydroxide may be used hydrates be used anhydride (LiOH) (LiOH ⁇ H 2 O) , but lithium hydroxide to be subjected to the single crystal growth process described later, which is dehydrated Is preferred.
  • the molten salt raw material does not contain a compound other than lithium hydroxide, and substantially consists of only lithium hydroxide.
  • lithium hydroxide since lithium hydroxide has the property of absorbing carbon dioxide in the atmosphere to form lithium carbonate, it may contain a trace amount of lithium carbonate as an impurity.
  • lithium hydroxide alone as a molten salt raw material from the viewpoint of oxidizing power. It is better not to include oxides, hydroxides such as potassium hydroxide and sodium hydroxide, metal salts such as lithium nitrate, etc. because they may affect the oxidizing power of lithium hydroxide.
  • the mixing ratio of the metal-containing raw material and the molten salt raw material may be appropriately selected according to the ratio of Li and metal element contained in the lithium-containing composite oxide to be produced.
  • the molten salt raw material plays the role of maintaining the oxidation state of the molten salt as well as the supply source of lithium. Therefore, the molten salt raw material contains lithium exceeding the theoretical composition of lithium contained in the lithium-containing composite oxide to be produced.
  • the theoretical composition of lithium contained in the target lithium-containing complex oxide (Li of lithium-containing complex oxide / Li of molten salt raw material) with respect to lithium contained in the molten salt raw material may be less than 1 in molar ratio.
  • Li in the lithium-containing composite oxide / Li in the molten salt raw material is preferably 0.01 to 0.4 in molar ratio, and in this case, single crystal particles are Easy to obtain in single particles. More preferably, it is 0.02 to 0.3, and it is 0.04 to 0.2. If the molar ratio of Li in the lithium-containing composite oxide to Li in the molten salt raw material is less than 0.01, the amount of the lithium-containing composite oxide to be formed is smaller than the amount of the molten salt raw material used Not desirable in terms of efficiency.
  • Li of the lithium-containing composite oxide / Li of the molten salt raw material is 0.4 or less in molar ratio, the molten salt for dispersing the metal-containing raw material is sufficiently present, and the lithium-containing composite oxide in the molten salt Aggregation is suppressed, which in turn makes it difficult to produce polycrystalline particles.
  • the drying step is mainly intended to dehydrate lithium hydroxide monohydrate, but even when using anhydrous lithium hydroxide, when using a highly hygroscopic compound as the metal-containing material.
  • the drying process is effective.
  • the water present in the molten salt composed of the molten salt raw material containing lithium hydroxide in the single crystal growth step has a very high pH.
  • the single crystal growth step is carried out in the presence of high pH water, the water may come in contact with the crucible, and depending on the type of crucible, the component of the crucible may be eluted into the molten salt although the amount is small.
  • the drying step the water content of the raw material mixture is removed, which leads to the elution suppression of the components of the crucible in the single crystal growth step. Further, by removing water from the raw material mixture in the drying step, it is possible to prevent the water from boiling and scattering of the molten salt in the single crystal growth step. If a vacuum drier is used in the drying step, vacuum drying may be performed at 80 ° C. to 150 ° C. for 2 hours to 24 hours.
  • the single crystal growth step is a step in which the reaction is carried out in the molten salt composed of the molten salt raw material.
  • the single crystal growth step is performed at a reaction temperature of 650 ° C. to 900 ° C., and the reaction temperature corresponds to the temperature of the molten salt.
  • the reaction temperature By setting the reaction temperature to 650 ° C. to 900 ° C., a single crystal having a high crystallinity and consisting of a lithium-containing composite oxide belonging to the layered rock salt structure is grown.
  • the reaction temperature is less than 650 ° C., it is not desirable because particles having a small particle size are easily formed.
  • a further desirable reaction temperature is 675 ° C. or more, further 700 ° C. or more.
  • the upper limit of the reaction temperature is less than the decomposition temperature of lithium hydroxide, preferably 900 ° C. or less, and more preferably 875 ° C. or less.
  • a reaction temperature of 700 ° C. to 900 ° C. is particularly desirable because growth of a single crystal is performed under stable conditions.
  • the reaction in the molten salt in a relatively low temperature range of 850 ° C. or less and further 825 ° C. or less suppresses the formation of impurities. The presence of impurities is believed to reduce the thermal stability of the lithium-containing composite oxide powder. The thermal stability of the lithium-containing composite oxide powder will be described in detail later.
  • the atmosphere for performing the single crystal growth step is not particularly limited and may be performed in the air.
  • an oxygen-containing atmosphere such as the atmosphere
  • a lithium-containing composite oxide having a layered rock salt structure can be easily obtained in a single phase.
  • the oxygen gas concentration in the atmosphere is 50 volumes It is preferable to set the percentage to not more than 15% by volume to 25% by volume.
  • the cooling step is a step of cooling the molten salt after the single crystal growth step.
  • it is desirable to cool the molten salt at a slow rate from the reaction temperature to the melting point of the molten salt or to room temperature from the viewpoint of causing the single crystal particles to grow large.
  • a cooling rate of 100 ° C./hour or less, and further 60 ° C./hour or less is desirable. Therefore, in the cooling step, it is desirable to adjust the cooling rate and gradually cool while keeping the high temperature molten salt after the reaction completed in the heating furnace.
  • the lower limit of the cooling rate is not particularly limited, a very slow cooling rate of, for example, less than 15 ° C./hour is not desirable because production efficiency is not good. Since the molten salt solidifies upon cooling, a mixture of the synthesized lithium-containing composite oxide and the molten salt is obtained as a solid after the cooling step.
  • the recovery step is a step of recovering the produced lithium-containing composite oxide from the solid after cooling. Specifically, it may be a separation and recovery step of dissolving the molten salt solidified in the cooling step in a polar protic solvent and separating the lithium-containing composite oxide generated in the single crystal growth step from the solidified molten salt. .
  • the polar protic solvent is adopted in this step because it can dissolve the solidified molten salt (that is, lithium hydroxide).
  • Specific examples of the polar protic solvent include pure water such as ion-exchanged water, alcohols such as ethanol, etc. One of these may be used alone or in combination of two or more. Good.
  • the solidified molten salt is easily dissolved in the polar protic solvent, and the lithium-containing composite oxide which is hardly soluble in the polar protic solvent remains soluble in the solvent. Therefore, the molten salt and the lithium-containing composite oxide are easily separated.
  • the method for recovering the lithium-containing composite oxide is not particularly limited, but the lithium-containing composite oxide can be recovered by centrifuging or filtering the solution. The recovered lithium-containing composite oxide may be dried. In the recovery step, the powdery lithium-containing composite oxide can be obtained by lightly pulverizing as necessary.
  • a proton substitution step may be performed in which part of Li of the lithium-containing composite oxide powder is replaced with hydrogen (H).
  • part of Li is easily replaced with H by bringing the lithium-containing composite oxide powder after the recovery step into contact with a solvent such as diluted acid.
  • a firing step of firing the lithium-containing composite oxide powder recovered in the recovery step may be performed.
  • the firing temperature is preferably 400 ° C. to 800 ° C. and more preferably 400 ° C. to 700 ° C. If the calcination temperature is 400 ° C. or more, improvement of the characteristics of the lithium-containing composite oxide powder as a positive electrode active material can be expected. However, if the firing temperature exceeds 700 ° C., aggregation occurs, which is not desirable. It is desirable to hold at this firing temperature for at least 20 minutes and further for 0.5 hour to 6 hours.
  • the firing may be performed in an oxygen-containing atmosphere.
  • the firing step may be performed in an oxygen-containing atmosphere, for example, in the atmosphere, in a gas atmosphere containing oxygen gas and / or ozone gas. In the case of an atmosphere containing oxygen gas, the oxygen gas concentration is preferably 20% by volume to 100% by volume, and more preferably 50% by volume to 100% by volume.
  • the lithium-containing composite oxide powder of the present invention can be used as a positive electrode active material for a secondary battery such as a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery.
  • a secondary battery such as a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery.
  • the non-aqueous electrolyte secondary battery using the positive electrode active material containing the said lithium containing complex oxide powder is demonstrated below.
  • the non-aqueous electrolyte secondary battery mainly includes a positive electrode, a negative electrode, and a non-aqueous electrolyte. Further, as in a general non-aqueous electrolyte secondary battery, a separator interposed between the positive electrode and the negative electrode is provided.
  • the positive electrode includes a positive electrode active material capable of inserting and releasing lithium ions, and a binder for binding the positive electrode active material. Furthermore, a conductive aid may be included.
  • the positive electrode active material may be a general non-aqueous electrolytic solution secondary, to the extent that the effect obtained by the present invention is not adversely affected by the above lithium-containing composite oxide powder alone or together with the above-mentioned lithium-containing composite oxide powder. It may also include one or more other positive electrode active materials used in the battery.
  • the binder and the conductive additive are not particularly limited as long as they can be used in general non-aqueous electrolyte secondary batteries.
  • the conductive aid is for securing the electrical conductivity of the electrode, and it is, for example, a mixture of one or more kinds of carbon substance powder such as carbon black, acetylene black and graphite as the conductive aid Can be used.
  • the binder plays the role of anchoring the positive electrode active material and the conductive additive, and as the binder, for example, fluorine-containing resin such as polyvinylidene fluoride, polytetrafluoroethylene, fluororubber, polypropylene, polyethylene, etc. A thermoplastic resin etc. can be used.
  • the negative electrode to be opposed to the positive electrode can be formed by forming a sheet of metal lithium which is a negative electrode active material or by pressing the sheet into a current collector network such as nickel or stainless steel. Instead of lithium metal, lithium alloys or lithium compounds can also be used. Further, as in the case of the positive electrode, a negative electrode comprising a negative electrode active material capable of inserting and extracting lithium ions and a binder may be used.
  • the negative electrode active material it is possible to use, for example, a calcined product of an organic compound such as natural graphite, artificial graphite, or a phenol resin, or a powder of a carbon material such as coke. Similar to the positive electrode, a fluorine-containing resin, a thermoplastic resin or the like can be used as the binder.
  • an active material layer formed by binding at least a positive electrode active material or a negative electrode active material with a binder is generally attached to a current collector. Therefore, the positive electrode and the negative electrode can be formed by the following method.
  • a composition for forming an electrode mixture layer containing an active material and a binder, and optionally a conductive auxiliary agent is prepared, and a suitable solvent is added to the composition for forming an electrode mixture layer to form a paste. After the paste is applied to the surface of the current collector, the current collector and the paste applied to the current collector are dried to form an electrode mixture layer on the current collector, and electrode combination is performed to increase the electrode density if necessary.
  • the material layer can be compressed to form the positive and negative electrodes.
  • a porous or non-porous conductive substrate made of a metal material such as stainless steel, titanium, nickel, aluminum, copper or the like or a conductive resin can be mentioned.
  • the porous conductive substrate include a mesh body, a net body, a punching sheet, a lath body, a porous body, a foam, a fiber group molded body such as a non-woven fabric, and the like.
  • non-porous conductive substrates include foils, sheets, films and the like.
  • metal mesh or metal foil can be used as a current collector.
  • a method of applying a composition for forming an electrode mixture layer to a current collector a conventionally known method such as a doctor blade or a bar coater may be used.
  • NMP N-methyl-2-pyrrolidone
  • MIBK methyl isobutyl ketone
  • non-aqueous electrolytic solution a general organic solvent-based electrolytic solution in which an electrolyte is dissolved in an organic solvent may be used.
  • the lithium-containing composite oxide powder of the present invention as a positive electrode active material, the decomposition of a general electrolytic solution used in a non-aqueous electrolytic solution secondary battery is suppressed.
  • the organic solvent preferably contains a chain ester in terms of loading characteristics.
  • chain esters include chain carbonates represented by dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and organic solvents such as ethyl acetate and methyl propionate.
  • These linear esters may be used alone or in combination of two or more, and in particular, for the improvement of low temperature properties, the above linear esters occupy 50% by volume or more in the total organic solvent.
  • an organic solvent in which an ester having a high dielectric constant (dielectric constant: 30 or more) is mixed with the above-mentioned chain ester rather than consisting only of the above chain ester.
  • esters include, for example, cyclic carbonates represented by ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate, ⁇ -butyrolactone, ethylene glycol sulfite and the like, and ethylene carbonate and propylene are particularly preferred.
  • Esters of cyclic structure such as carbonate are preferred.
  • Such an ester having a high dielectric constant is preferably contained in an amount of 10% by volume or more, particularly 20% by volume or more in the total organic solvent from the viewpoint of discharge capacity. Further, from the viewpoint of load characteristics, the ester having a high dielectric constant is preferably contained in an amount of 40% by volume or less in the total organic solvent, and more preferably 30% by volume or less.
  • an electrolyte solution containing ethylene carbonate and ethyl methyl carbonate is widely used, and the use of the lithium-containing composite oxide powder of the present invention is also effective for such an electrolyte solution.
  • LiClO 4 LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 ( SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), etc.
  • LiPF 6 and LiC 4 F 9 SO 3 which can obtain good charge / discharge characteristics as an electrolyte are preferably used.
  • the concentration of the electrolyte in the electrolytic solution is not particularly limited, but the concentration of the electrolyte is 0.3 mol / dm 3 to 1.7 mol / dm 3 , and in particular 0.4 mol / dm 3 to 1.5 mol / l. it is preferably dm 3 approximately.
  • the non-aqueous electrolyte may contain an aromatic compound.
  • aromatic compound benzenes having an alkyl group such as cyclohexylbenzene or t-butylbenzene, biphenyl or fluorobenzenes are preferably used.
  • the separator preferably has sufficient strength and can hold a large amount of electrolytic solution, and from such a viewpoint, polypropylene, polyethylene, copolymers of propylene and ethylene, etc. are made of polyolefin with a thickness of 5 ⁇ m to 50 ⁇ m. Microporous films and non-woven fabrics are preferably used. In particular, when a thin separator of 5 ⁇ m to 20 ⁇ m is used, the battery characteristics are easily deteriorated during charge / discharge cycles or high temperature storage, and the safety is also reduced. Since the lithium ion secondary battery used as the active material is excellent in stability and safety, the battery can be stably functioned even using such a thin separator.
  • the shape of the non-aqueous electrolyte secondary battery configured by the above components can be various shapes such as a cylindrical shape, a laminated shape, and a coin shape.
  • a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body.
  • the positive electrode current collector and the negative electrode current collector are connected to the positive electrode terminal and the negative electrode terminal leading to the outside by means of a current collection lead etc.
  • the electrode body is impregnated with the above-mentioned electrolytic solution and sealed in a battery case. The electrolyte secondary battery is completed.
  • the non-aqueous electrolyte secondary battery using the lithium-containing composite oxide powder of the present invention as a positive electrode active material has a high heat stability, and is excellent in safety because the thermal stability of the lithium-containing composite oxide powder is high.
  • the thermal stability of the lithium-containing composite oxide powder is high.
  • the crystal structure is broken and the thermal stability is lowered due to the storage or release of lithium ions accompanying charge and discharge.
  • oxygen gas is likely to be generated as the temperature rises due to heat generation. Therefore, enhancing the thermal stability of the positive electrode active material to suppress the generation of oxygen gas leads to prevention of battery ignition and thermal runaway.
  • the lithium-containing composite oxide powder of the present invention has high thermal stability as compared to those synthesized by a general solid phase method. It is considered that this is because the lithium-containing composite oxide powder of the present invention was synthesized under the conditions in which the generation of impurities is suppressed.
  • the thermal stability is defined by numerical values, the lithium-containing composite oxide powder in a charged state has an exothermic peak observed when performing thermal analysis while raising the temperature by differential scanning calorimetry (DSC measurement) It is desirable to show 700 J / g or less when calorific value is computed from (transition of the heat flow of a differential scanning calorimetry curve). More preferably, it is more than 0 J / g and not more than 675 J / g.
  • the maximum value of heat flow is preferably observed in the range of 250 to 350 ° C. and 270 to 350 ° C., more preferably 280 to 350 ° C.
  • the lithium-containing composite oxide powder in the as-synthesized state by the above-described production method of the present invention does not generate heat only by raising the temperature. Therefore, the calorific value is a value obtained by performing DSC measurement on a lithium-containing composite oxide powder in a charged state, particularly in a fully charged state.
  • the lithium-containing composite oxide powder of the present invention exhibits a low calorific value of 700 J / g or less even in a fully charged state.
  • “full charge state” means that when the non-aqueous electrolyte secondary battery is charged up to a predetermined voltage by constant current-constant voltage charge (CCCV charge), CV charge is performed for a predetermined time to obtain a non-aqueous electrolyte. It means that the secondary battery is charged.
  • CCCV charge constant current-constant voltage charge
  • the non-aqueous electrolyte secondary battery using the lithium-containing composite oxide powder obtained by the manufacturing method of the present invention described above is not only in the field of communication equipment such as mobile phones and personal computers, but also in the field of automobiles Can also be suitably used.
  • this non-aqueous electrolyte secondary battery is mounted on a vehicle, the non-aqueous electrolyte secondary battery can be used as a power source for an electric vehicle.
  • the raw material mixture was put in a crucible, and the raw material mixture was put in a vacuum drying vessel and vacuum dried at 120 ° C. for 12 hours. Thereafter, the vacuum drying vessel was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, and the crucible was immediately transferred to an electric furnace at 800 ° C. and heated in the air at 800 ° C. for 12 hours. At this time, the raw material mixture in the crucible was melted to form a molten salt, and a red product was precipitated in the crucible.
  • the crucible was removed from the electric furnace.
  • the cooling rate was 39 ° C./hour because it took 20 hours for the molten salt to solidify and reach room temperature (25 ° C.).
  • the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water.
  • the water became a red suspension because the product was insoluble in water.
  • the red suspension was filtered to give a clear filtrate and a red solid filtrate on filter paper.
  • the resulting filtrate was filtered with thorough washing with acetone.
  • the washed red solid was vacuum dried at 120 ° C. for about 12 hours, and then ground using a mortar and a pestle to obtain a red powder.
  • the obtained red powder was evaluated for average valence of Mn by emission spectral analysis (ICP) and redox titration. As a result, the composition was confirmed to be Li 2 MnO 3 . Moreover, the X-ray-diffraction (XRD) measurement which used the CuK alpha ray was performed about the obtained red powder. According to XRD, it was found that the obtained compound had a layered rock salt structure.
  • Active oxygen content (%) ⁇ (2 x V2-V1) x 0.00080 / amount of sample ⁇ x 100
  • the units of V1 and V2 are mL, and the unit of sample amount is g.
  • the average valence of Mn was calculated from the amount of Mn in the sample measured by ICP and the amount of active oxygen.
  • Example 2 Synthesis of Li 2 MnO 3
  • Li 2 MnO 3 was synthesized under the same conditions as in Example 1 except that 0.20 mol of anhydrous lithium hydroxide (LiOH, 4.79 g) was used as the molten salt raw material instead of lithium hydroxide monohydrate. did.
  • anhydrous lithium hydroxide LiOH, 4.79 g
  • the raw material mixture was put in a crucible, and the raw material mixture was put in a vacuum drying container and vacuum dried at 120 ° C. for 12 hours. Thereafter, the vacuum drying vessel was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, and the crucible was immediately transferred to an electric furnace at 800 ° C. and heated in the air at 800 ° C. for 12 hours. At this time, the raw material mixture in the crucible was melted to form a molten salt, and a black product was precipitated in the crucible.
  • the crucible was removed from the electric furnace.
  • the cooling rate was 52 ° C./hour because it took 15 hours for the molten salt to solidify and reach room temperature (25 ° C.).
  • the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water.
  • the water was a black suspension because the product was insoluble in water.
  • the black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper.
  • the resulting filtrate was filtered with thorough washing with acetone.
  • the washed black solid was vacuum dried at 120 ° C. for about 12 hours, and then ground using a mortar and a pestle to obtain a black powder.
  • the obtained black powder was subjected to XRD measurement using a CuK ⁇ ray. According to XRD, the obtained compound was found to be a layered rock salt structure LiCoO 2 .
  • the raw material mixture was put in a crucible, and the raw material mixture was put in a vacuum drying container and vacuum dried at 120 ° C. for 12 hours. Thereafter, the vacuum drying vessel was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, and the crucible was immediately transferred to an electric furnace at 800 ° C. and heated in the air at 800 ° C. for 12 hours. At this time, the raw material mixture in the crucible was melted to form a molten salt, and a black product was precipitated in the crucible.
  • the crucible was removed from the electric furnace.
  • the cooling rate was 32 ° C./hour because it took 24 hours for the molten salt to solidify and reach room temperature (25 ° C.).
  • the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water.
  • the water was a black suspension because the product was insoluble in water.
  • the black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper.
  • the resulting filtrate was filtered with thorough washing with acetone.
  • the washed black solid was vacuum dried at 120 ° C. for about 12 hours, and then ground using a mortar and a pestle to obtain a black powder.
  • the obtained black powder was subjected to XRD measurement using a CuK ⁇ ray. According to XRD, the obtained compound was found to be a layered rock salt structure LiNiO 2 .
  • Example 5 Synthesis of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 A raw material mixture was prepared by mixing 0.30 mol of lithium hydroxide (LiOH.H 2 O, 12.6 g) as a molten salt raw material and a precursor (1.0 g) as a metal compound raw material. Below, the synthetic
  • the transition metal element content of this precursor 1g is 0.013 mol.
  • the raw material mixture was put in a crucible, and the raw material mixture was put in a vacuum drying container and vacuum dried at 120 ° C. for 12 hours. Thereafter, the vacuum drying vessel was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, and the crucible was immediately transferred to an electric furnace at 800 ° C. and heated in the air at 800 ° C. for 6 hours. At this time, the raw material mixture in the crucible was melted to form a molten salt, and a black product was precipitated in the crucible.
  • the crucible was removed from the electric furnace.
  • the cooling rate was 52 ° C./hour because it took 15 hours for the molten salt to solidify and reach room temperature (25 ° C.).
  • the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water.
  • the water was a black suspension because the product was insoluble in water.
  • the black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper.
  • the resulting filtrate was filtered with thorough washing with acetone.
  • the washed black solid was vacuum dried at 120 ° C. for about 6 hours, and then ground using a mortar and a pestle to obtain a black powder.
  • the obtained black powder was subjected to emission spectral analysis (ICP) and mean valence analysis of Mn by redox titration. As a result, the composition was confirmed to be LiCo 1/3 Ni 1/3 Mn 1/3 O 2 . Moreover, the X-ray-diffraction (XRD) measurement which used the CuK alpha ray was performed about the obtained black powder. According to XRD, it was found that the obtained compound had a layered rock salt structure.
  • Comparative Example 1 Synthesis of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 LiCo 1/3 Ni 1/3 Mn 1/3 O 2 was synthesized under the same conditions as Example 5 except that heating was performed in the atmosphere at 600 ° C. for 6 hours in an electric furnace at 600 ° C. However, the cooling rate was 115 ° C./hour because it took 5 hours to reach 600 ° C. to 25 ° C.
  • the powder thus synthesized was subjected to emission spectral analysis (ICP) and mean valence analysis of Mn by redox titration. As a result, the composition was confirmed to be LiCo 1/3 Ni 1/3 Mn 1/3 O 2 . Moreover, the XRD measurement which used the CuK alpha ray was performed about the synthesize
  • grains was measured from the image of several particle
  • the results were as follows.
  • the extremely small particles attached to the particle surface as shown in FIG. 1 are ungrown by-products, but were regarded as one particle including the particles on the surface, and the average primary particle size was calculated.
  • Example 1 (Li 2 MnO 3 powder): 16 ⁇ m
  • Example 2 (Li 2 MnO 3 powder): 14 ⁇ m
  • Example 3 (LiCoO 2 powder): 9 ⁇ m
  • Example 4 (LiNiO 2 powder): 5 ⁇ m
  • Example 5 (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 powder): 2 ⁇ m Comparative Example 1 (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 Fine Powder): 100 nm
  • the specific surface area of the lithium-containing composite oxide powder of each example and comparative example was measured using the BET method based on low temperature low humidity physical adsorption. In the BET method, the adsorbate was nitrogen. The results were as follows.
  • Example 1 (Li 2 MnO 3 powder): 0.74 m 2 / g
  • Example 2 (Li 2 MnO 3 powder): 0.96 m 2 / g
  • Example 3 (LiCoO 2 powder): 1.72 m 2 / g
  • Example 4 (LiNiO 2 powder): 2.03 m 2 / g
  • Example 5 (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 powder): 5.58 m 2 / g Comparative Example 1 (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 Fine Powder): 20.6 m 2 / g
  • the lithium-containing composite oxide powder of each example was observed by a transmission electron microscope (TEM), and limited field electron diffraction was performed under the conditions of an accelerating voltage of 200 kV to identify and evaluate a single crystal.
  • TEM transmission electron microscope
  • regular diffraction points showing the characteristics of a single crystal were observed no matter which particle was observed.
  • diffraction patterns obtained from different positions in the same plane in one particle were observed as diffraction points showing the same plane index. Therefore, it was found that the obtained particles were single crystal particles without grain boundaries.
  • a mixture was prepared by mixing any lithium-containing composite oxide, acetylene black as a conductive additive, and polytetrafluoroethylene (PTFE) as a binder at a mass ratio of 50:40:10. Subsequently, this mixture was crimped
  • the negative electrode opposed to the positive electrode was graphite with a diameter of 14 mm and a thickness of 30 ⁇ m.
  • a 20 ⁇ m-thick microporous polyethylene film was sandwiched between the positive electrode and the negative electrode as a separator to obtain an electrode body battery.
  • the electrode battery was housed in a battery case (CR2032 coin cell manufactured by Takasen Co., Ltd.).
  • a non-aqueous electrolytic solution in which LiPF 6 is dissolved at a concentration of 1.0 mol / L in a mixed solvent of ethylene carbonate and ethyl methyl carbonate mixed at a volume ratio of 1: 2 is injected into the battery case I got a secondary battery.
  • the charge / discharge test was performed at room temperature (25 ° C.) using the produced lithium ion secondary battery.
  • the charging was performed at a rate of 0.2 C to constant current charging to a predetermined voltage (4.2 V in the case of # 03) described in Table 1, and then charging was performed at a constant voltage to a current value of 0.02 C.
  • the discharge was performed at a rate of 0.2 C up to the predetermined voltage (2.0 V for # 03) described in Table 1.
  • the charge and discharge curves of the first cycle (first cycle) of the lithium ion secondary battery # 03 and the lithium ion secondary battery # 05 are shown in FIGS. 7 and 8.
  • the capacity maintenance rate discharge capacity at 50th cycle / discharge capacity at first cycle
  • the results are shown in Table 1.
  • the # 03 to # 05 lithium ion secondary batteries had a very high capacity retention after 50 cycles.
  • the use of a powder containing single crystal particles consisting of a lithium-containing composite oxide as a positive electrode active material results in suppression of particle collapse and electrolyte decomposition during charge and discharge, resulting in cycles. It is believed that the characteristics have improved.
  • the # 05 lithium ion secondary battery has a charge cutoff voltage of 4.4 V, which is higher than that of the # 03 and # 04 lithium ion secondary batteries, and is considered to be likely to cause deterioration of the electrolytic solution.
  • the lithium ion secondary battery had a capacity retention rate of 98% after 50 cycles, and was excellent in cycle characteristics. Also, it was found that the initial discharge capacity of each of the lithium ion secondary batteries was large, and the average voltage was high as seen in FIGS. 7 and 8.
  • Example 5 synthesized according to the above procedure and the conventional lithium-containing composite oxide powder (that is, LiCo 1/3 Ni 1/3 Mn 1/3 DSC measurement was performed for the O 2 powder according to the following procedure.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 powder commercially available as a battery material and synthesized as a conventional lithium-containing composite oxide powder and synthesized by a solid phase method (the primary particle size observed by SEM is 200 ⁇ 500 ⁇ m) was used.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 has a crystalline structure with low thermal stability due to the release of Li. Therefore, LiCo 1/3 Ni 1/3 Mn 1/3 O to prepare a lithium ion secondary battery including a positive electrode containing a 2, LiCo 1/3 after the charge state Ni 1/3 Mn 1/3 O 2 DSC measurements were made on
  • Example 5 or the conventional lithium-containing composite oxide as a positive electrode active material, acetylene black as a conductive additive, polyvinylidene fluoride as a binder are mixed in a mass ratio of 88: 6: 6, and a slurry-like mixture And Next, this mixture was applied to one side of an aluminum foil as a current collector, pressed and shaped, and then heated at 120 ° C. for 6 hours. Thus, a positive electrode provided with a positive electrode active material layer on the surface of the current collector was obtained. As a negative electrode opposed to the positive electrode, a graphite negative electrode having a capacity sufficient to absorb lithium moving from the positive electrode to the negative electrode was used.
  • the lithium ion secondary battery was produced using the electrode produced by said procedure. Between a positive electrode and a negative electrode in which a positive electrode active material layer containing lithium-containing composite oxide powder and a negative electrode active material layer containing graphite were opposed, a polypropylene porous film as a separator was sandwiched to prepare an electrode body. This electrode body was sealed with an electrolytic solution and an aluminum film to form a laminate cell. At the time of sealing, two aluminum films are sealed by removing heat by welding except for a part of the periphery, and an electrode body and an electrolytic solution are further added from the opening and the vacuum is applied while opening. The part was sealed airtight. At this time, the tips of the current collectors on the positive electrode side and the negative electrode side were made to project from the edge of the film so as to be connectable to the external terminal.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 by charging the two types of lithium ion secondary batteries produced according to the following procedure at room temperature (25 ° C.) to fully charge the battery.
  • room temperature 25 ° C.
  • a lithium-containing composite oxide lacking Li was obtained.
  • the constant current-constant voltage charging was performed to 4.2 V at a rate of 0.2 C until the fully charged state was reached. Constant voltage charging was performed for 2.5 hours after completion of constant current charging, and charging was completed.
  • the lithium ion secondary battery was disassembled and the positive electrode was taken out. The removed positive electrode was washed with dimethyl carbonate. After drying the washed positive electrode, the positive electrode active material layer including the lithium-containing composite oxide powder after releasing lithium in an argon atmosphere was peeled off from the positive electrode current collector. 5 mg of the peeled positive electrode active material layer was weighed, and stored in a SUS pressure cell (manufactured by Shimadzu Corporation).
  • 2.8 ⁇ L of a solution of LiPF 6 dissolved at a concentration of 1.0 mol / L in a mixed solvent of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate mixed at a volume ratio of 3: 3: 4 is added to a SUS pressure cell Sealed.
  • the sample thus prepared contained a positive electrode active material, a conductive additive, a binder and an electrolytic solution, and contained the same components as the positive electrode of the above lithium ion secondary battery charged.
  • the differential scanning calorimetry curve of the sample prepared by the above-mentioned procedure and contained in the SUS pressure cell was measured using a high sensitivity differential scanning calorimeter ThermoPlus EVO / DSC 8230 (manufactured by Rigaku Corporation). DSC measurement was performed by raising the temperature of the sample from room temperature to 450 ° C. at a heating rate of 5 ° C./min in a nitrogen gas atmosphere. A differential scanning calorimetry curve in the range of 150 to 350 ° C. is shown in FIG. At 150 ° C. or lower and 350 ° C. or higher, which were not shown, no remarkable exothermic peak was observed.
  • the heat is generated from the area (area of the exothermic peak) of the part surrounded by the differential scanning calorific curve and the dotted line shown in FIG.
  • the amount (unit: J) was calculated and converted to the calorific value (unit: J / g) per unit mass of the lithium-containing composite oxide powder.
  • the dotted line shown in FIG. 9 is a background simply added to the differential scanning calorific value curve in order to explain the area corresponding to the calorific value. Background and calorific value are actually introduced and calculated by software attached to the calorimeter.
  • the calorific value of the lithium-containing composite oxide per unit mass can be determined from the mass of the lithium-containing composite oxide contained in the sample Unit: J / g was calculated. The results are shown below.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 powder of Example 5 650 J / g
  • Conventional LiCo 1/3 Ni 1/3 Mn 1/3 O 2 powder 750 J / g

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Abstract

L'invention concerne une poudre d'oxyde complexe contenant du lithium idéale comme substance active d'électrode positive d'une cellule secondaire à électrolyte non aqueux, telle qu'une cellule secondaire lithium-ion ; elle concerne également un procédé pour sa production. Cette poudre d'oxyde complexe contenant du lithium est caractérisée en ce qu'elle est produite par le procédé en sel fondu, en ce qu'elle contient des grains monocristallins formés à partir d'un oxyde complexe contenant du lithium qui comprend au moins du lithium et un ou plusieurs autres types d'éléments métalliques différents et qui présente une structure cristalline appartenant à une structure de sel gemme stratifiée, et en ce qu'elle présente une taille de grains primaires moyenne entre 200 nm et 30 µm. Cette poudre d'oxyde complexe contenant du lithium est produite en faisant réagir des matériaux de départ contenant du métal à une température de réaction entre 650 et 900ºC dans un sel fondu d'hydroxyde de lithium.
PCT/JP2012/004070 2011-06-24 2012-06-22 Poudre d'oxyde complexe contenant du lithium et son procédé de production WO2012176471A1 (fr)

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JP2013175302A (ja) * 2012-02-23 2013-09-05 Toyota Industries Corp 複合酸化物の製造方法、二次電池用正極活物質および二次電池
KR20170117063A (ko) * 2015-02-17 2017-10-20 도다 고교 가부시끼가이샤 비수전해질 이차 전지용 정극 활물질, 비수전해질 이차 전지
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JP2020077611A (ja) * 2018-09-11 2020-05-21 エコプロ ビーエム カンパニー リミテッドＥｃｏｐｒｏ Ｂｍ Ｃｏ．， Ｌｔｄ． リチウム二次電池用正極活物質およびこれを含むリチウム二次電池
CN112886006A (zh) * 2021-04-28 2021-06-01 蜂巢能源科技有限公司 一种单晶高镍正极材料及其制备方法和应用
JP2022520866A (ja) * 2019-02-28 2022-04-01 エスエム ラブ コーポレーション リミテッド 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP7464735B2 (ja) 2020-05-25 2024-04-09 蜂巣能源科技股▲ふん▼有限公司 コバルトフリー複合正極材料及びその製造方法
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JP2013175302A (ja) * 2012-02-23 2013-09-05 Toyota Industries Corp 複合酸化物の製造方法、二次電池用正極活物質および二次電池
KR20170117063A (ko) * 2015-02-17 2017-10-20 도다 고교 가부시끼가이샤 비수전해질 이차 전지용 정극 활물질, 비수전해질 이차 전지
KR102636863B1 (ko) 2015-02-17 2024-02-19 도다 고교 가부시끼가이샤 비수전해질 이차 전지용 정극 활물질, 비수전해질 이차 전지
WO2018088320A1 (fr) * 2016-11-08 2018-05-17 本田技研工業株式会社 Électrode pour batteries rechargeables à électrolyte non aqueux, et batteries rechargeables à électrolyte non aqueux comprenant celle-ci
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JP2020077611A (ja) * 2018-09-11 2020-05-21 エコプロ ビーエム カンパニー リミテッドＥｃｏｐｒｏ Ｂｍ Ｃｏ．， Ｌｔｄ． リチウム二次電池用正極活物質およびこれを含むリチウム二次電池
US11990616B2 (en) 2018-09-11 2024-05-21 Ecopro Bm Co., Ltd. Positive electrode active material for lithium secondary battery and lithium secondary battery including the same
JP2022520866A (ja) * 2019-02-28 2022-04-01 エスエム ラブ コーポレーション リミテッド 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP7258372B2 (ja) 2019-02-28 2023-04-17 エスエム ラブ コーポレーション リミテッド 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP7464735B2 (ja) 2020-05-25 2024-04-09 蜂巣能源科技股▲ふん▼有限公司 コバルトフリー複合正極材料及びその製造方法
CN112886006A (zh) * 2021-04-28 2021-06-01 蜂巢能源科技有限公司 一种单晶高镍正极材料及其制备方法和应用

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